Spirobifluorene compounds for organic electroluminescent devices

ABSTRACT

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

The present invention relates to materials for use in electronicdevices, in particular in organic electroluminescent devices, and toelectronic devices comprising these materials.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are employed as functional materials isdescribed, for example, in U.S. Pat. Nos. 4,539,507, 5,151,629, EP0676461 and WO 98/27136. The emitting materials employed here areincreasingly organometallic complexes which exhibit phosphorescenceinstead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75,4-6).

In accordance with the prior art, the hole-transport materials used inthe hole-transport layer or in the hole-injection layer are, inparticular, triarylamine derivatives which frequently contain at leasttwo triarylamino groups or at least one triarylamino group and at leastone carbazole group. These compounds are frequently derived fromdiarylamino-substituted triphenylamines (TPA type), fromdiarylamino-substituted biphenyl derivatives (TAD type) or combinationsof these base compounds. Furthermore, for example, use is made ofspirobifluorene derivatives which are substituted in the 2,7- or2,2′,7,7′-position by two or four diarylamino groups (for example inaccordance with EP 676461 or U.S. Pat. No. 7,714,145). Furthermore knownare spirobifluorene derivatives which are substituted in the4,4′-position in each case by diphenylamino groups. In the case of thesecompounds, there is furthermore a need for improvement both in the caseof fluorescent and in the case of phosphorescent OLEDs, in particularwith respect to efficiency, lifetime and operating voltage on use in anorganic electroluminescent device.

The object of the present invention is to provide compounds which aresuitable for use in a fluorescent or phosphorescent OLED, in particulara phosphorescent OLED, for example as hole-transport material in ahole-transport or exciton-blocking layer or as matrix material in anemitting layer.

Surprisingly, it has been found that certain compounds described belowin greater detail achieve this object and result in significantimprovements in the organic electroluminescent device, in particularwith respect to the lifetime, the efficiency and the operating voltage.This applies to phosphorescent and fluorescent electroluminescentdevices, especially on use of the compounds according to the inventionas hole-transport material or as matrix material. The materialsgenerally have high thermal stability and can therefore be sublimedwithout decomposition and without a residue. The present inventiontherefore relates to these materials and to electronic devices whichcomprise compounds of this type.

In particular, it is a surprising result that very good results are alsoobtained, in particular, with aromatic monoamines, since hole-transportmaterials containing at least two nitrogen atoms are generally employedin organic electroluminescent devices.

The present invention therefore relates to a compound of the followingformula (1).

where the following applies to the symbols and indices used:

-   -   Ar¹ is on each occurrence, identically or differently, an        aromatic or heteroaromatic ring system having 6 to 60 C atoms,        selected from the group consisting of fluorene, spirobifluorene,        biphenyl, terphenyl, quaterphenyl, carbazole, dibenzofuran and        dibenzothiophene, each of which may also be substituted by one        or more radicals R⁵; Ar¹ and Ar² here may also be connected to        one another by a group E;    -   Ar² is on each occurrence, identically or differently, an        aromatic or heteroaromatic ring system having 6 to 60 C atoms,        which may in each case also be substituted by one or more        radicals R⁵; Ar¹ and Ar² here may also be connected to one        another by a group E;    -   Ar^(S) is on each occurrence, identically or differently, an        aromatic or heteroaromatic ring system having 6 to 60 C atoms,        which may in each case also be substituted by one or more        radicals R⁵;    -   E is on each occurrence, identically or differently, a single        bond, C(R⁵)₂, NR⁵, O or S;    -   R¹, R², R³, R⁴ are selected on each occurrence, identically or        differently, from the group consisting of H, D, F, Cl, Br, I,        CN, Si(R⁶)₃, a straight-chain alkyl, alkoxy or thioalkyl group        having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or        thioalkyl group having 3 to 40 C atoms, each of which may be        substituted by one or more radicals R⁶, where in each case one        or more non-adjacent CH₂ groups may be replaced by Si(R⁶)₂,        C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, S or CONR⁶ and where one or        more H atoms may be replaced by D, F, Cl, Br or I, an aromatic        or heteroaromatic ring system having 6 to 60 C atoms, which may        in each case be substituted by one or more radicals R⁶, an        aryloxy or heteroaryloxy group having 5 to 60 aromatic ring        atoms, which may be substituted by one or more radicals R⁶, or        an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring        atoms, which may in each case be substituted by one or more        radicals R⁶, where two or more adjacent substituents R¹ or R² or        R³ or R⁴ may optionally form a mono- or polycyclic, aliphatic        ring system, which may be substituted by one or more radicals        R⁶;    -   R⁵ is selected on each occurrence, identically or differently,        from the group consisting of H, D, F, Cl, Br, I, CN, Si(R⁶)₃, a        straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C        atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group        having 3 to 40 C atoms, each of which may be substituted by one        or more radicals R⁶, where in each case one or more non-adjacent        CH₂ groups may be replaced by Si(R⁶)₂, C═NR⁶, P(═O)(R⁶), SO,        SO₂, NR⁶, O, S or CONR⁶ and where one or more H atoms may be        replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic        ring system having 6 to 60 C atoms, which may in each case be        substituted by one or more radicals R⁶, an aryloxy or        heteroaryloxy group having 5 to 60 aromatic ring atoms, which        may be substituted by one or more radicals R⁶, or an aralkyl or        heteroaralkyl group having 5 to 60 aromatic ring atoms, which        may in each case be substituted by one or more radicals R⁶,        where two or more adjacent substituents R⁵ may optionally form a        mono- or polycyclic, aliphatic ring system, which may be        substituted by one or more radicals R⁶;    -   R⁶ is selected from the group consisting of H, D, F, an        aliphatic hydro-carbon radical having 1 to 20 C atoms or an        aromatic or heteroaromatic ring system having 5 to 30 C atoms,        in which one or more H atoms may be replaced by D or F, where        two or more adjacent substituents R⁶ may form a mono- or        polycyclic, aliphatic ring system with one another;    -   i is on each occurrence, identically or differently, 0 or 1;    -   m is 0, 1 or 2;    -   n is on each occurrence, identically or differently, 0, 1, 2, 3        or 4;    -   p, q are on each occurrence, identically or differently, 0 or 1;    -   r, s are on each occurrence, identically or differently, 0, 1,        2, 3 or 4, where p+r≤4 and q+s≤4.

In addition, the present invention relates to a compound of a formula(1), with the proviso that the following definitions apply to groups Ar¹and Ar² instead of the definitions above:

groups Ar¹ and Ar² are connected to each other via a group E, as definedabove, and

groups Ar¹ and Ar² are, identically or differently on each occurrence,an aromatic or heteroaromatic ring system having 6 to 60 C atoms, whichmay in each case also be substituted by one or more radicals R⁵.

An aryl group in the sense of this invention is taken to mean either asimple aromatic ring, i.e. benzene, or a condensed (anellated) arylgroup, for example naphthalene or phenanthrene. By contrast, aromaticgroups linked to one another by a single bond, such as, for example,biphenyl or fluorene, are not referred to as an aryl group, but insteadas an aromatic ring system.

A heteroaryl group in the sense of the present invention comprises atleast one heteroatom in the aromatic ring, preferably a heteroatomselected from N, O and S. A heteroaryl group may comprise only a simpleheteroaromatic ring, such as e.g. pyridine, triazine, or thiophene, orit may be a condensed (annelated) heteroaryl group, such as quinoline orcarbazole.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system, where the aromatic ring system may be builtup e.g. from benzene, naphthalene, phenanthrene, fluorene andspirobifluorene or combinations of these groups. An aromatic ring systemin the sense of this invention is, in particular, also intended to betaken to mean a system in which, in addition, a plurality of aryl groupsis linked to one another directly or via a carbon atom. Thus, forexample, systems such as biphenyl, terphenyl, quaterphenyl, fluorene,9,9′-spirobifluorene, 9,9-diarylfluorene, etc., in particular, are alsointended to be taken to be aromatic ring systems in the sense of thisinvention. The aromatic ring system here by definition contains no aminogroups. Triarylamino groups are thus not covered by the definition of anaromatic ring system.

An analogous definition applies to the term heteroaromatic ring system,which is to be understood to be a combination of two or moreinterconnected aryl or heteroaryl groups, at least one of them being aheteroaryl group.

An aralkyl group is to be understood to be an alkyl group which issubstituted by an aryl group, where the aryl group is defined as above,and the alkyl group may have 1 to 20 C atoms, and may be substituted asdefined above for alkyl groups, and may have one or more CH₂ groupsreplaced as defined above for alkyl groups. In the aralkyl group, thealkyl group is the group which bonds to the rest of the compound. Ananalogous definition applies to the term heteroaralkyl group, only thata heteroaryl group is present instead of an aryl group.

An aryloxy group is to be understood to be an aryl group bonded via adivalent (ether) oxygen atom. An analogous definition applies to theterm heteroaryloxy group, only that a heteroaryl group is presentinstead of an aryl group.

For the purposes of the present invention, an aliphatic hydrocarbonradical or an alkyl group or an alkenyl or alkynyl group, which maytypically contain 1 to 40 or also 1 to 20 C atoms and in which, inaddition, individual H atoms or CH₂ groups may be substituted by theabove-mentioned groups, is preferably taken to mean the radicals methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl,neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl,2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl,ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl,cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

An alkoxy group having 1 to 40 C atoms is preferably taken to meanmethoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy,n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy or2,2,2-trifluoroethoxy.

A thioalkyl group having 1 to 40 C atoms is taken to mean, inparticular, methylthio, ethylthio, n-propylthio, i-propylthio,n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio,s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio,cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio,trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio,ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio,hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio,octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio,pentynylthio, hexynyl-thio, heptynylthio or octynylthio.

In general, alkyl, alkoxy or thioalkyl groups in accordance with thepresent invention can be straight-chain, branched or cyclic, where oneor more non-adjacent CH₂ groups may be replaced by the above-mentionedgroups; furthermore, one or more H atoms may also be replaced by D, F,Cl, Br, I, CN or NO₂, preferably F, Cl or CN, further preferably F orCN, particularly preferably CN.

In a preferred embodiment of the invention, p+q=0 or 1. The compoundaccording to the invention thus preferably contains one or twodiarylamino groups.

In a preferred embodiment, m, s, r, and n are identically or differentlyon each occurrence 0 or 1, more preferably 0.

According to a further preferred embodiment of the invention, not morethan one index i in the formula (1) is 1. More preferably, the index iis generally equal to 0. For the case that the index i is 0, it is to beunderstood that the spirobifluorene and the nitrogen atom are directlyconnected.

In a preferred embodiment of the invention, the compound of the formula(1) is selected from the compounds of the following formulae (2) to(10),

where the symbols and indices used have the meanings given above.

For the compounds according to formulae (2) to (10) above, it ispreferred that i=0.

In a particularly preferred embodiment of the invention, the compoundsof the formulae (2) to (10) are selected from the compounds of thefollowing formulae (2a) to (10a),

where the symbols and indices used have the meanings given above.

For the compounds according to formulae (2a) to (10a) above, it ispreferred that i=0.

Very particular preference is given to the compounds of the followingformulae (2b) to (10b),

where the symbols used have the meanings given above.

In a particularly preferred embodiment of the invention, the compoundaccording to the invention contains only one diarylamino group —NAr¹Ar².This thus preferably relates to compounds of the formulae (2), (5) and(8) or (2a), (5a) and (8a) or (2b), (5b) and (8b).

In a further preferred embodiment of the invention, the diarylaminogroups —NAr¹Ar² are bonded in the 4-position or in the 4- and4′-position of the spirobifluorene. This thus preferably relates to thecompounds of the formulae (2) and (3) or (2a) and (3a) or (2b) and (3b).

Very particular preference is given to the compounds of the formula (2)or (2a) or (2b).

In a further preferred embodiment of the invention, Ar² is selected,identically or differently, from the group consisting of fluorene,spirobifluorene, biphenyl, terphenyl, quaterphenyl, carbazole,dibenzofuran and dibenzothiophene, each of which may be substituted byone or more radicals R⁵.

The groups Ar¹ and Ar² here are preferably selected, identically ordifferently on each occurrence, from the groups of the followingformulae (11) to (66),

where the dashed bond indicates the bond to the nitrogen, and the groupsmay be substituted by one or more radicals R⁵, but are preferablyunsubstituted.

R⁵ in the groups of the formulae (20) to (23), (53) and (54) preferablystands, identically or differently, for an alkyl group having 1 to 10 Catoms, in particular for methyl, or a phenyl group, which may besubstituted by one or more radicals R⁶.

Preferred groups Ar¹ and Ar² are selected, identically or differently oneach occurrence, from the group consisting of the above-mentionedformulae (11), (13), (16), (20), (28), (29), (33), (34), (35), (37),(38), (39), (40), (44), (48), (49), (51) and (59). All possiblecombinations of these groups are equally possible here.

Particularly preferred is that Ar¹ and Ar² are selected, identically ordifferently on each occurrence, from the group consisting of theabove-mentioned formulae (11), (13), (20), (29), (35), (38), (39), (49),(51) and (59).

Furthermore, R⁵ in the groups of the formulae (28) to (31) and (40) to(43) and (55) to (58) and (63) to (66) preferably stands for a phenylgroup, an ortho-biphenyl group, a meta-biphenyl group, a para-biphenylgroup, a terphenyl group, a 1-naphthyl group, or a 2-naphthyl groupwhich may be substituted by one or more radicals R⁶.

Preferably, Ar¹ and Ar² are selected, identically or differently on eachoccurrence, from the groups of the formulae (11), (20) and (24), whichmay be substituted by one or more radicals R⁵.

At least one of the groups Ar¹ and Ar² is particularly preferably agroup of the formula (11) or (20). Very particularly preferably, Ar¹stands for a group of the formula (11) and Ar² stands for a group of theformula (20).

The two groups Ar¹ and Ar² of the above-mentioned formulae (11) to (66)which are bonded to the nitrogen may be combined with one another asdesired.

In a preferred embodiment of the invention, the groups Ar¹ and Ar² areselected differently from one another.

If the groups Ar¹ and Ar² in the compounds of the formula (1) and (2) to(10) or the preferred embodiments are linked to one another by a groupE, the group —NAr¹Ar² preferably has the structure of one of thefollowing formulae (67) to (74),

where the symbols used have the meanings given above, and the dashedbond indicates the bond to the spirobifluorene. These groups may also besubstituted by one or more radicals R⁵, but are preferablyunsubstituted.

R⁵ in the group of the formula (68) and (72) preferably stands,identically or differently, for an alkyl group having 1 to 10 C atoms,in particular for methyl, or a phenyl group, which may be substituted byone or more radicals R⁶.

Furthermore, R⁵ in the group of the formula (71) and (73) preferablystands for a phenyl group, which may be substituted by one or moreradicals R⁶.

Preferred substituted embodiments of the formula (13) are the followingformulae (13a) to (13f), a preferred embodiment of the formula (16) arethe formulae (16a) and (16b), preferred embodiments of the formula (20)are the following formulae (20a) to (20l), preferred embodiments of theformula (21) are the following formulae (21a) to (21g), preferredembodiments of the formula (22) are the following formulae (22a), (22b),(22c) and (22d), and preferred embodiments of the formula (23) are thefollowing formulae (23a), (23b), (23c) and (23d),

where the dashed bond indicates the bond to the nitrogen.

Group Ar^(S) is preferably, identically or differently on eachoccurrence, selected from aromatic or heteroaromatic ring systems having6 to 18 aromatic ring atoms, which may in each case also be substitutedby one or more radicals R⁵.

Particularly preferable groups Ar^(S) are selected from the groups offormulae (Ar^(S)-1) to (Ar^(S)-15) below:

where the dashed bonds indicates the bonds to the spirobifluorene and tothe amine, and where the groups may be substituted at each free positionby a group R⁵ but are preferably unsubstituted.

In a preferred embodiment of the invention, R¹ to R⁴ are selected,identically or differently on each occurrence, from the group consistingof H, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 Catoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 Catoms, each of which may be substituted by one or more radicals R⁶,where one or more non-adjacent CH₂ groups may be replaced by O and whereone or more H atoms may be replaced by F, an aromatic or heteroaromaticring system having 6 to 24 aromatic ring atoms, which may in each casebe substituted by one or more radicals R⁶.

In a particularly preferred embodiment of the invention, R¹ to R⁴ areselected on each occurrence, identically or differently, from the groupconsisting of H, F, a straight-chain alkyl group having 1 to 5 C atomsor a branched or cyclic alkyl group having 3 to 6 C atoms, an aromaticor heteroaromatic ring system having 5 to 18 aromatic ring atoms, whichmay in each case be substituted by one or more radicals R⁶.

Most preferably, R¹ to R⁴ are selected, identically or differently, fromH, F, phenyl, methyl and tert-butyl.

R¹ to R⁴ in the compounds of the formulae (1) and (2) to (10) and (2a)to (10a) are very particularly preferably selected, identically ordifferently on each occurrence, from the group consisting of H, F,methyl, tert-butyl, and phenyl.

In a further preferred embodiment of the invention, the radical R⁵ whichis bonded to Ar¹ or Ar² or Ar^(S) is selected, identically ordifferently on each occurrence, from the group consisting of H, F, CN, astraight-chain alkyl group having 1 to 10 C atoms, a branched or cyclicalkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ringsystem having 5 to 24 aromatic ring atoms, each of which may besubstituted by one or more radicals R⁶.

In a particularly preferred embodiment of the invention, the radical R⁵which is bonded to Ar¹ or Ar² or Ar^(S) is selected, identically ordifferently on each occurrence, from the group consisting of H, astraight-chain alkyl group having 1 to 5 C atoms, a branched or cyclicalkyl group having 3 to 6 C atoms or an aromatic or heteroaromatic ringsystem having 5 to 24 aromatic ring atoms, each of which may besubstituted by one or more radicals R⁶.

The radicals R¹ to R⁶ here preferably contain no condensed aryl orheteroaryl groups in which more than two aromatic or heteroaromaticsix-membered rings are condensed directly onto one another, i.e., forexample, no anthracene or pyrene groups. The radicals R¹ to R⁶particularly preferably contain absolutely no condensed aryl orheteroaryl groups in which aromatic or heteroaromatic six-membered ringsare condensed directly onto one another, i.e. also, for example, nonaphthalene groups.

It may furthermore be preferred for the two substituents R⁵ in the9-position of a fluorene together to form a cycloalkyl ring, preferablyhaving 3 to 8 C atoms, particularly preferably having 5 or 6 C atoms.

Likewise, the two substituents R⁵ in formula (68) and (72) may form aring system with one another and thus form a spiro system, for example acycloalkyl ring, preferably having 3 to 8 C atoms, particularlypreferably having 5 or 6 C atoms.

For compounds which are processed by vacuum evaporation, the alkylgroups preferably have not more than four C atoms, particularlypreferably not more than 1 C atom. For compounds which are processedfrom solution, suitable compounds are also those which are substitutedby linear, branched or cyclic alkyl groups having up to 10 C atoms orwhich are substituted by oligoarylene groups, for example ortho-, meta-,para- or branched terphenyl or quaterphenyl groups.

In a preferred embodiment of the invention, R⁶ is selected, identicallyor differently on each occurrence, from the group consisting of H, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms or an aromatic ring systemhaving 6 to 24 C atoms. R⁶ is particularly preferably, identically ordifferently on each occurrence, H or a methyl group, very particularlypreferably H.

Particular preference is given to compounds of the formulae (1) and (2)to (10) and (2a) to (10a) and (2b) to (10b), in which the preferredembodiments mentioned above occur simultaneously. Particular preferenceis therefore given to compounds for which:

-   -   Ar¹, Ar² are, identically or differently, a group of one of the        formulae (11) to (66);        -   or —NAr¹Ar² stands for a group of one of the formulae (67)            to (74);    -   E is on each occurrence, identically or differently, a single        bond or C(R¹)₂, N(R¹), O or S;    -   R¹ to R⁴ are selected, identically or differently on each        occurrence, from the group consisting of H, F, CN, a        straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a        branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms,        each of which may be substituted by one or more radicals R⁶,        where one or more non-adjacent CH₂ groups may be replaced by O        and where one or more H atoms may be replaced by F, an aromatic        or heteroaromatic ring system having 6 to 24 aromatic ring        atoms, which may in each case be substituted by one or more        radicals R⁶;    -   R⁵ is, if the radical R⁵ is bonded to Ar¹ or Ar² or Ar^(S),        selected, identically or differently on each occurrence, from        the group consisting of H, F, CN, a straight-chain alkyl group        having 1 to 10 C atoms, a branched or cyclic alkyl group having        3 to 10 C atoms or an aromatic or heteroaromatic ring system        having 5 to 24 aromatic ring atoms, each of which may be        substituted by one or more radicals R⁶;        -   or R⁵ which is bonded to the carbon bridge in the            formulae (20) to (23), (53), (54), (68) and (72) is,            identically or differently, an alkyl group having 1 to 10 C            atoms, in particular methyl, or a phenyl group, which may be            substituted by one or more radicals R⁶;        -   or R⁵ which is bonded to the nitrogen bridge in the            formulae (28) to (31), (40) to (43) or (55) to (58), (63) to            (66), (71) and (73) is a phenyl group, which may be            substituted by one or more radicals R⁶;    -   R⁶ is selected on each occurrence, identically or differently,        from the group consisting of H, a straight-chain alkyl group        having 1 to 10 C atoms or a branched or cyclic alkyl group        having 3 to 10 C atoms or an aromatic ring system having 6 to 24        C atoms;    -   i is 0;    -   m is 0 or 1, preferably 0;    -   n is 0 or 1;    -   p+q is 0 or 1;    -   r is 0 or 1;    -   s is 0 or 1.

Examples for preferred structures for compounds according to formula (1)are listed in the following. The compounds are based on the basicstructures of formulae (2a), (5a) and (8a).

basic structure Ar¹ of Ar² of Formula of formula i= formula formula(2a-1-1) (2a) 0 (11) (11) (2a-1-2) (2a) 0 (11) (13) (2a-1-3) (2a) 0 (11)(20) (2a-1-4) (2a) 0 (11) (29) (2a-1-5) (2a) 0 (11) (35) (2a-1-6) (2a) 0(11) (38) (2a-1-7) (2a) 0 (11) (39) (2a-1-8) (2a) 0 (11) (49) (2a-1-9)(2a) 0 (11) (51) (2a-1-10) (2a) 0 (11) (59) (2a-1-11) (2a) 0 (13) (13)(2a-1-12) (2a) 0 (13) (20) (2a-1-13) (2a) 0 (13) (29) (2a-1-14) (2a) 0(13) (35) (2a-1-15) (2a) 0 (13) (38) (2a-1-16) (2a) 0 (13) (39)(2a-1-17) (2a) 0 (13) (49) (2a-1-18) (2a) 0 (13) (51) (2a-1-19) (2a) 0(13) (59) (2a-1-20) (2a) 0 (20) (20) (2a-1-21) (2a) 0 (20) (29)(2a-1-22) (2a) 0 (20) (35) (2a-1-23) (2a) 0 (20) (38) (2a-1-24) (2a) 0(20) (39) (2a-1-25) (2a) 0 (20) (49) (2a-1-26) (2a) 0 (20) (51)(2a-1-27) (2a) 0 (20) (59) (2a-1-28) (2a) 0 (29) (29) (2a-1-29) (2a) 0(29) (35) (2a-1-30) (2a) 0 (29) (38) (2a-1-31) (2a) 0 (29) (39)(2a-1-32) (2a) 0 (29) (49) (2a-1-33) (2a) 0 (29) (51) (2a-1-34) (2a) 0(29) (59) (2a-1-35) (2a) 0 (35) (35) (2a-1-36) (2a) 0 (35) (38)(2a-1-37) (2a) 0 (35) (39) (2a-1-38) (2a) 0 (35) (49) (2a-1-39) (2a) 0(35) (51) (2a-1-40) (2a) 0 (35) (59) (2a-1-41) (2a) 0 (38) (38)(2a-1-42) (2a) 0 (38) (39) (2a-1-43) (2a) 0 (38) (49) (2a-1-44) (2a) 0(38) (51) (2a-1-45) (2a) 0 (38) (59) (2a-1-46) (2a) 0 (39) (39)(2a-1-47) (2a) 0 (39) (49) (2a-1-48) (2a) 0 (39) (51) (2a-1-49) (2a) 0(39) (59) (2a-1-50) (2a) 0 (49) (49) (2a-1-51) (2a) 0 (49) (51)(2a-1-52) (2a) 0 (49) (59) (2a-1-53) (2a) 0 (51) (51) (2a-1-54) (2a) 0(51) (59) (2a-1-55) (2a) 0 (59) (59) (2a-2-1) (2a) 1 (11) (11) (2a-2-2)(2a) 1 (11) (13) (2a-2-3) (2a) 1 (11) (20) (2a-2-4) (2a) 1 (11) (29)(2a-2-5) (2a) 1 (11) (35) (2a-2-6) (2a) 1 (11) (38) (2a-2-7) (2a) 1 (11)(39) (2a-2-8) (2a) 1 (11) (49) (2a-2-9) (2a) 1 (11) (51) (2a-2-10) (2a)1 (11) (59) (2a-2-11) (2a) 1 (13) (13) (2a-2-12) (2a) 1 (13) (20)(2a-2-13) (2a) 1 (13) (29) (2a-2-14) (2a) 1 (13) (35) (2a-2-15) (2a) 1(13) (38) (2a-2-16) (2a) 1 (13) (39) (2a-2-17) (2a) 1 (13) (49)(2a-2-18) (2a) 1 (13) (51) (2a-2-19) (2a) 1 (13) (59) (2a-2-20) (2a) 1(20) (20) (2a-2-21) (2a) 1 (20) (29) (2a-2-22) (2a) 1 (20) (35)(2a-2-23) (2a) 1 (20) (38) (2a-2-24) (2a) 1 (20) (39) (2a-2-25) (2a) 1(20) (49) (2a-2-26) (2a) 1 (20) (51) (2a-2-27) (2a) 1 (20) (59)(2a-2-28) (2a) 1 (29) (29) (2a-2-29) (2a) 1 (29) (35) (2a-2-30) (2a) 1(29) (38) (2a-2-31) (2a) 1 (29) (39) (2a-2-32) (2a) 1 (29) (49)(2a-2-33) (2a) 1 (29) (51) (2a-2-34) (2a) 1 (29) (59) (2a-2-35) (2a) 1(35) (35) (2a-2-36) (2a) 1 (35) (38) (2a-2-37) (2a) 1 (35) (39)(2a-2-38) (2a) 1 (35) (49) (2a-2-39) (2a) 1 (35) (51) (2a-2-40) (2a) 1(35) (59) (2a-2-41) (2a) 1 (38) (38) (2a-2-42) (2a) 1 (38) (39)(2a-2-43) (2a) 1 (38) (49) (2a-2-44) (2a) 1 (38) (51) (2a-2-45) (2a) 1(38) (59) (2a-2-46) (2a) 1 (39) (39) (2a-2-47) (2a) 1 (39) (49)(2a-2-48) (2a) 1 (39) (51) (2a-2-49) (2a) 1 (39) (59) (2a-2-50) (2a) 1(49) (49) (2a-2-51) (2a) 1 (49) (51) (2a-2-52) (2a) 1 (49) (59)(2a-2-53) (2a) 1 (51) (51) (2a-2-54) (2a) 1 (51) (59) (2a-2-55) (2a) 1(59) (59) (5a-1-1) (5a) 0 (11) (11) (5a-1-2) (5a) 0 (11) (13) (5a-1-3)(5a) 0 (11) (20) (5a-1-4) (5a) 0 (11) (29) (5a-1-5) (5a) 0 (11) (35)(5a-1-6) (5a) 0 (11) (38) (5a-1-7) (5a) 0 (11) (39) (5a-1-8) (5a) 0 (11)(49) (5a-1-9) (5a) 0 (11) (51) (5a-1-10) (5a) 0 (11) (59) (5a-1-11) (5a)0 (13) (13) (5a-1-12) (5a) 0 (13) (20) (5a-1-13) (5a) 0 (13) (29)(5a-1-14) (5a) 0 (13) (35) (5a-1-15) (5a) 0 (13) (38) (5a-1-16) (5a) 0(13) (39) (5a-1-17) (5a) 0 (13) (49) (5a-1-18) (5a) 0 (13) (51)(5a-1-19) (5a) 0 (13) (59) (5a-1-20) (5a) 0 (20) (20) (5a-1-21) (5a) 0(20) (29) (5a-1-22) (5a) 0 (20) (35) (5a-1-23) (5a) 0 (20) (38)(5a-1-24) (5a) 0 (20) (39) (5a-1-25) (5a) 0 (20) (49) (5a-1-26) (5a) 0(20) (51) (5a-1-27) (5a) 0 (20) (59) (5a-1-28) (5a) 0 (29) (29)(5a-1-29) (5a) 0 (29) (35) (5a-1-30) (5a) 0 (29) (38) (5a-1-31) (5a) 0(29) (39) (5a-1-32) (5a) 0 (29) (49) (5a-1-33) (5a) 0 (29) (51)(5a-1-34) (5a) 0 (29) (59) (5a-1-35) (5a) 0 (35) (35) (5a-1-36) (5a) 0(35) (38) (5a-1-37) (5a) 0 (35) (39) (5a-1-38) (5a) 0 (35) (49)(5a-1-39) (5a) 0 (35) (51) (5a-1-40) (5a) 0 (35) (59) (5a-1-41) (5a) 0(38) (38) (5a-1-42) (5a) 0 (38) (39) (5a-1-43) (5a) 0 (38) (49)(5a-1-44) (5a) 0 (38) (51) (5a-1-45) (5a) 0 (38) (59) (5a-1-46) (5a) 0(39) (39) (5a-1-47) (5a) 0 (39) (49) (5a-1-48) (5a) 0 (39) (51)(5a-1-49) (5a) 0 (39) (59) (5a-1-50) (5a) 0 (49) (49) (5a-1-51) (5a) 0(49) (51) (5a-1-52) (5a) 0 (49) (59) (5a-1-53) (5a) 0 (51) (51)(5a-1-54) (5a) 0 (51) (59) (5a-1-55) (5a) 0 (59) (59) (5a-2-1) (5a) 1(11) (11) (5a-2-2) (5a) 1 (11) (13) (5a-2-3) (5a) 1 (11) (20) (5a-2-4)(5a) 1 (11) (29) (5a-2-5) (5a) 1 (11) (35) (5a-2-6) (5a) 1 (11) (38)(5a-2-7) (5a) 1 (11) (39) (5a-2-8) (5a) 1 (11) (49) (5a-2-9) (5a) 1 (11)(51) (5a-2-10) (5a) 1 (11) (59) (5a-2-11) (5a) 1 (13) (13) (5a-2-12)(5a) 1 (13) (20) (5a-2-13) (5a) 1 (13) (29) (5a-2-14) (5a) 1 (13) (35)(5a-2-15) (5a) 1 (13) (38) (5a-2-16) (5a) 1 (13) (39) (5a-2-17) (5a) 1(13) (49) (5a-2-18) (5a) 1 (13) (51) (5a-2-19) (5a) 1 (13) (59)(5a-2-20) (5a) 1 (20) (20) (5a-2-21) (5a) 1 (20) (29) (5a-2-22) (5a) 1(20) (35) (5a-2-23) (5a) 1 (20) (38) (5a-2-24) (5a) 1 (20) (39)(5a-2-25) (5a) 1 (20) (49) (5a-2-26) (5a) 1 (20) (51) (5a-2-27) (5a) 1(20) (59) (5a-2-28) (5a) 1 (29) (29) (5a-2-29) (5a) 1 (29) (35)(5a-2-30) (5a) 1 (29) (38) (5a-2-31) (5a) 1 (29) (39) (5a-2-32) (5a) 1(29) (49) (5a-2-33) (5a) 1 (29) (51) (5a-2-34) (5a) 1 (29) (59)(5a-2-35) (5a) 1 (35) (35) (5a-2-36) (5a) 1 (35) (38) (5a-2-37) (5a) 1(35) (39) (5a-2-38) (5a) 1 (35) (49) (5a-2-39) (5a) 1 (35) (51)(5a-2-40) (5a) 1 (35) (59) (5a-2-41) (5a) 1 (38) (38) (5a-2-42) (5a) 1(38) (39) (5a-2-43) (5a) 1 (38) (49) (5a-2-44) (5a) 1 (38) (51)(5a-2-45) (5a) 1 (38) (59) (5a-2-46) (5a) 1 (39) (39) (5a-2-47) (5a) 1(39) (49) (5a-2-48) (5a) 1 (39) (51) (5a-2-49) (5a) 1 (39) (59)(5a-2-50) (5a) 1 (49) (49) (5a-2-51) (5a) 1 (49) (51) (5a-2-52) (5a) 1(49) (59) (5a-2-53) (5a) 1 (51) (51) (5a-2-54) (5a) 1 (51) (59)(5a-2-55) (5a) 1 (59) (59) (8a-1-1) (8a) 0 (11) (11) (8a-1-2) (8a) 0(11) (13) (8a-1-3) (8a) 0 (11) (20) (8a-1-4) (8a) 0 (11) (29) (8a-1-5)(8a) 0 (11) (35) (8a-1-6) (8a) 0 (11) (38) (8a-1-7) (8a) 0 (11) (39)(8a-1-8) (8a) 0 (11) (49) (8a-1-9) (8a) 0 (11) (51) (8a-1-10) (8a) 0(11) (59) (8a-1-11) (8a) 0 (13) (13) (8a-1-12) (8a) 0 (13) (20)(8a-1-13) (8a) 0 (13) (29) (8a-1-14) (8a) 0 (13) (35) (8a-1-15) (8a) 0(13) (38) (8a-1-16) (8a) 0 (13) (39) (8a-1-17) (8a) 0 (13) (49)(8a-1-18) (8a) 0 (13) (51) (8a-1-19) (8a) 0 (13) (59) (8a-1-20) (8a) 0(20) (20) (8a-1-21) (8a) 0 (20) (29) (8a-1-22) (8a) 0 (20) (35)(8a-1-23) (8a) 0 (20) (38) (8a-1-24) (8a) 0 (20) (39) (8a-1-25) (8a) 0(20) (49) (8a-1-26) (8a) 0 (20) (51) (8a-1-27) (8a) 0 (20) (59)(8a-1-28) (8a) 0 (29) (29) (8a-1-29) (8a) 0 (29) (35) (8a-1-30) (8a) 0(29) (38) (8a-1-31) (8a) 0 (29) (39) (8a-1-32) (8a) 0 (29) (49)(8a-1-33) (8a) 0 (29) (51) (8a-1-34) (8a) 0 (29) (59) (8a-1-35) (8a) 0(35) (35) (8a-1-36) (8a) 0 (35) (38) (8a-1-37) (8a) 0 (35) (39)(8a-1-38) (8a) 0 (35) (49) (8a-1-39) (8a) 0 (35) (51) (8a-1-40) (8a) 0(35) (59) (8a-1-41) (8a) 0 (38) (38) (8a-1-42) (8a) 0 (38) (39)(8a-1-43) (8a) 0 (38) (49) (8a-1-44) (8a) 0 (38) (51) (8a-1-45) (8a) 0(38) (59) (8a-1-46) (8a) 0 (39) (39) (8a-1-47) (8a) 0 (39) (49)(8a-1-48) (8a) 0 (39) (51) (8a-1-49) (8a) 0 (39) (59) (8a-1-50) (8a) 0(49) (49) (8a-1-51) (8a) 0 (49) (51) (8a-1-52) (8a) 0 (49) (59)(8a-1-53) (8a) 0 (51) (51) (8a-1-54) (8a) 0 (51) (59) (8a-1-55) (8a) 0(59) (59) (8a-2-1) (8a) 1 (11) (11) (8a-2-2) (8a) 1 (11) (13) (8a-2-3)(8a) 1 (11) (20) (8a-2-4) (8a) 1 (11) (29) (8a-2-5) (8a) 1 (11) (35)(8a-2-6) (8a) 1 (11) (38) (8a-2-7) (8a) 1 (11) (39) (8a-2-8) (8a) 1 (11)(49) (8a-2-9) (8a) 1 (11) (51) (8a-2-10) (8a) 1 (11) (59) (8a-2-11) (8a)1 (13) (13) (8a-2-12) (8a) 1 (13) (20) (8a-2-13) (8a) 1 (13) (29)(8a-2-14) (8a) 1 (13) (35) (8a-2-15) (8a) 1 (13) (38) (8a-2-16) (8a) 1(13) (39) (8a-2-17) (8a) 1 (13) (49) (8a-2-18) (8a) 1 (13) (51)(8a-2-19) (8a) 1 (13) (59) (8a-2-20) (8a) 1 (20) (20) (8a-2-21) (8a) 1(20) (29) (8a-2-22) (8a) 1 (20) (35) (8a-2-23) (8a) 1 (20) (38)(8a-2-24) (8a) 1 (20) (39) (8a-2-25) (8a) 1 (20) (49) (8a-2-26) (8a) 1(20) (51) (8a-2-27) (8a) 1 (20) (59) (8a-2-28) (8a) 1 (29) (29)(8a-2-29) (8a) 1 (29) (35) (8a-2-30) (8a) 1 (29) (38) (8a-2-31) (8a) 1(29) (39) (8a-2-32) (8a) 1 (29) (49) (8a-2-33) (8a) 1 (29) (51)(8a-2-34) (8a) 1 (29) (59) (8a-2-35) (8a) 1 (35) (35) (8a-2-36) (8a) 1(35) (38) (8a-2-37) (8a) 1 (35) (39) (8a-2-38) (8a) 1 (35) (49)(8a-2-39) (8a) 1 (35) (51) (8a-2-40) (8a) 1 (35) (59) (8a-2-41) (8a) 1(38) (38) (8a-2-42) (8a) 1 (38) (39) (8a-2-43) (8a) 1 (38) (49)(8a-2-44) (8a) 1 (38) (51) (8a-2-45) (8a) 1 (38) (59) (8a-2-46) (8a) 1(39) (39) (8a-2-47) (8a) 1 (39) (49) (8a-2-48) (8a) 1 (39) (51)(8a-2-49) (8a) 1 (39) (59) (8a-2-50) (8a) 1 (49) (49) (8a-2-51) (8a) 1(49) (51) (8a-2-52) (8a) 1 (49) (59) (8a-2-53) (8a) 1 (51) (51)(8a-2-54) (8a) 1 (51) (59) (8a-2-55) (8a) 1 (59) (59)

The compounds of the list above have preferably as Ar^(S) and R¹ to R⁴the preferred embodiments of these groups which have been describedabove. More preferably, in the compounds listed above, Ar^(S) isselected from groups Ar^(S)-1 to Ar^(S)-15, as defined above. Morepreferably, in the compounds listed above, R¹ to R⁴ is selected,identically or differently, from H, F, phenyl, methyl and tert-butyl.

Examples of suitable compounds according to the invention are thecompounds shown in the following table:

The compounds according to the invention can be prepared by syntheticsteps known to the person skilled in the art, such as, for example,bromination, Ullmann arylation, Hartwig-Buchwald coupling, etc.

The syntheses generally start from the 1-, 3- or 4-halogenated, inparticular brominated, spirobifluorene derivatives, followed by a C—Ncoupling reaction, for example a Hartwig-Buchwald coupling or an Ullmanncoupling, for introduction of the diarylamino group. Analogously,another suitable leaving group, for example tosylate or triflate, can beused instead of the halogen. The synthesis of1-diarylaminospirobifluorene is shown in Scheme 1, where two differentaccess routes to the brominated starting compound are shown.

Analogously to the classical spiro synthesis shown above, thecorresponding spirobifluorene derivatives which are halogenated in the3- or 4-position can be synthesised by employing the corresponding 3- or4-halogen-substituted fluorenone as starting material. Likewise,corresponding substituted structures can also be synthesised entirelyanalogously.

In a modification of the process shown in Scheme 1 a, it is likewisepossible to perform the Buchwald coupling in a first step on thefluorenone, and then perform the addition of the metalated biphenyl andthe ring closure to the spirobifluorene afterwards. For further details,such synthesis process is shown in the working examples.

Spirobifluorene-carbazole compounds can be synthesized by Buchwaldcoupling of a carbazole with a halogen-substituted spirobifluorene, asshown in the working examples.

The present invention therefore furthermore relates to a process for thepreparation of a compound of the formula (1), characterised in that thediarylamino group is introduced by a C—N coupling reaction between a 1-or 3- or 4-halogenated spirobifluorene and a diarylamine.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, boronic acid or boronic acid ester, can be used asmonomers for the preparation of corresponding oligomers, dendrimers orpolymers. The oligomerisation or polymerisation here is preferablycarried out via the halogen functionality or the boronic acidfunctionality.

The invention therefore furthermore relates to oligomers, polymers ordendrimers comprising one or more compounds of the formula (1), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired positions in formula (1) substituted by R¹ to R⁵. Dependingon the linking of the compound of the formula (1), the compound is partof a side chain of the oligomer or polymer or part of the main chain. Anoligomer in the sense of this invention is taken to mean a compoundwhich is built up from at least three monomer units. A polymer in thesense of the invention is taken to mean a compound which is built upfrom at least ten monomer units. The polymers, oligomers or dendrimersaccording to the invention may be conjugated, partially conjugated ornon-conjugated. The oligomers or polymers according to the invention maybe linear, branched or dendritic. In the structures linked in a linearmanner, the units of the formula (1) may be linked directly to oneanother or linked to one another via a divalent group, for example via asubstituted or unsubstituted alkylene group, via a heteroatom or via adivalent aromatic or heteroaromatic group. In branched and dendriticstructures, three or more units of the formula (1) may, for example, belinked via a trivalent or polyvalent group, for example via a trivalentor polyvalent aromatic or hetero-aromatic group, to give a branched ordendritic oligomer or polymer. The same preferences as described abovefor compounds of the formula (1) apply to the recurring units of theformula (1) in oligomers, dendrimers and polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 00/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 06/061181), paraphenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 04/070772 or WO04/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 05/014689 or WO07/006383), cis- and trans-indenofluorenes (for example in accordancewith WO 04/041901 or WO 04/113412), ketones (for example in accordancewith WO 05/040302), phenanthrenes (for example in accordance with WO05/104264 or WO 07/017066) or also a plurality of these units. Thepolymers, oligomers and dendrimers usually also contain further units,for example emitting (fluorescent or phosphorescent) units, such as, forexample, vinyltriarylamines (for example in accordance with WO07/068325) or phosphorescent metal complexes (for example in accordancewith WO 06/003000), and/or charge-transport units, in particular thosebased on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (1) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;

(B) YAMAMOTO polymerisation;

(C) STILLE polymerisation; and

(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 02/067343 A1 and WO 2005/026144 A1.

The compounds according to the invention are suitable for use in anelectronic device. An electronic device here is taken to mean a devicewhich comprises at least one layer which comprises at least one organiccompound. However, the component here may also comprise inorganicmaterials or also layers built up entirely from inorganic materials.

The present invention therefore furthermore relates to the use of thecompounds according to the invention in an electronic device, inparticular in an organic electroluminescent device.

The present invention still furthermore relates to an electronic devicecomprising at least one compound according to the invention. Thepreferences stated above likewise apply to the electronic devices.

The electronic device is preferably selected from the group consistingof organic electroluminescent devices (organic light-emitting diodes,OLEDs), organic integrated circuits (O-ICs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic solar cells (O-SCs),organic dye-sensitised solar cells (ODSSCs), organic optical detectors,organic photoreceptors, organic field-quench devices (O-FQDs),light-emitting electrochemical cells (LECs), organic laser diodes(O-lasers) and organic plasmon emitting devices (D. M. Koller et al.,Nature Photonics 2008, 1-4), but preferably organic electroluminescentdevices (OLEDs), particularly preferably phosphorescent OLEDs.

The organic electroluminescent devices and the light-emittingelectrochemical cells can be employed for various applications, forexample for mono-chromatic or polychromatic displays, for lightingapplications or for medical and/or cosmetic applications, for example inphototherapy.

The organic electroluminescent device comprises a cathode, an anode andat least one emitting layer. Apart from these layers, it may alsocomprise further layers, for example in each case one or morehole-injection layers, hole-transport layers, hole-blocking layers,electron-transport layers, electron-injection layers, exciton-blockinglayers, electron-blocking layers and/or charge-generation layers.Interlayers, which have, for example, an exciton-blocking function, maylikewise be introduced between two emitting layers. However, it shouldbe pointed out that each of these layers does not necessarily have to bepresent.

The organic electroluminescent device here may comprise one emittinglayer or a plurality of emitting layers. If a plurality of emissionlayers is present, these preferably have in total a plurality ofemission maxima between 380 nm and 750 nm, resulting overall in whiteemission, i.e. various emitting compounds which are able to fluoresce orphosphoresce are used in the emitting layers. Particular preference isgiven to systems having three emitting layers, where the three layersexhibit blue, green and orange or red emission (for the basic structuresee, for example, WO 2005/011013). It is possible here for all emittinglayers to be fluorescent or for all emitting layers to be phosphorescentor for one or more emitting layers to be fluorescent and one or moreother layers to be phosphorescent.

The compound according to the invention in accordance with theembodiments indicated above can be employed here in different layers,depending on the precise structure. Preference is given to an organicelectroluminescent device comprising a compound of the formula (1) orthe preferred embodiments as hole-transport material in a hole-transportor hole-injection or exciton-blocking or electron-blocking layer or asmatrix material for fluorescent or phosphorescent emitters in anemitting layer, in particular for phosphorescent emitters. The preferredembodiments indicated above also apply to the use of the materials inorganic electronic devices.

In a preferred embodiment of the invention, the compound of the formula(1) or the preferred embodiments is employed as hole-transport orhole-injection-material in a hole-transport or hole-injection layer. Theemitting layer here can be fluorescent or phosphorescent. Ahole-injection layer in the sense of the present invention is a layerwhich is directly adjacent to the anode. A hole-transport layer in thesense of the present invention is a layer which is located between ahole-injection layer and an emitting layer.

In still a further preferred embodiment of the invention, the compoundof the formula (1) or the preferred embodiments is employed in anexciton-blocking layer. An exciton-blocking layer is taken to mean alayer which is directly adjacent to an emitting layer on the anode side.

The compound of the formula (1) or the preferred embodiments isparticularly preferably employed in a hole-transport or exciton-blockinglayer.

In an embodiment of the invention, the compound of the formula (1) orthe preferred embodiments is used in a hole-transport or -injectionlayer in combination with a layer which comprises a hexaazatriphenylenederivative, in particular hexacyanohexaazatriphenylene (for example inaccordance with EP 1175470). Thus, for example, preference is given to acombination which looks as follows: anode—hexaazatriphenylenederivative—hole-transport layer, where the hole-transport layercomprises one or more compounds of the formula (1) or the preferredembodiments. It is likewise possible in this structure to use aplurality of successive hole-transport layers, where at least onehole-transport layer comprises at least one compound of the formula (1)or the preferred embodiments. A further preferred combination looks asfollows: anode—hole-transport layer—hexaazatriphenylenederivative—hole-transport layer, where at least one of the twohole-transport layers comprises one or more compounds of the formula (1)or the preferred embodiments. It is likewise possible in this structureto use a plurality of successive hole-transport layers instead of onehole-transport layer, where at least one hole-transport layer comprisesat least one compound of the formula (1) or the preferred embodiments.

If the compound according to formula (1) is employed as a holetransporting material in a hole transporting layer, a hole injectionlayer, an exciton blocking layer or an electron blocking layer, thecompound may be used as a pure material, i.e. in a proportion of 100% inthe layer, or it may be used in combination with one or more othermaterials. According to a preferred embodiment, in this case, the one orother compound which is used in combination with the compound accordingto formula (1) is a p-dopant. Preferred p-dopants to be used areelectron acceptor compounds, preferably such electron acceptor compoundswhich can oxidize one or more of the other compounds of the mixture.

The p-dopant is preferably present in a concentration of 0.1 to 20Vol-%, preferably 0.5 to 12 Vol-%, more preferably 1 to 8 Vol-% and mostpreferably 2 to 6 Vol-% in the layer comprising the compound accordingto the invention.

Particularly preferred p-dopants to be used in combination with thecompounds according to the invention are the compounds disclosed in oneor more of the following documents: WO 2011/073149, EP 1968131, EP2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, U.S. Pat.Nos. 8,044,390, 8057712, WO 2009/003455, WO 2010/094378, WO 2011/120709,US 2010/0096600 and WO 2012/095143.

Highly preferred p-dopants to be used in the devices according to theinvention are quinodimethanes, azaindenofluorendiones, azaphenalenes,azatriphenylenes, I₂, metal halogenides, preferably transition metalhalogenides, metal oxides, preferably transition metal oxides or metaloxides comprising at least one metal of the third main group, andtransition metal complexes, preferably complexes of Cu, Co, Ni, Pd or Ptwith ligands having at least one binding oxygen atom. Preferred arefurthermore transition metal oxides such as rhenium oxides, molybdenumoxides and tungsten oxides, more preferably Re₂O₇, MoO₃, WO₃ and ReO₃.

Preferred p-dopants are furthermore the following compounds:

In a further preferred embodiment of the invention, the compound of theformula (1) or the preferred embodiments is employed as matrix materialfor a fluorescent or phosphorescent compound, in particular for aphosphorescent compound, in an emitting layer. The organicelectroluminescent device here may comprise one emitting layer or aplurality of emitting layers, where at least one emitting layercomprises at least one compound according to the invention as matrixmaterial.

If the compound of the formula (1) or the preferred embodiments isemployed as matrix material for an emitting compound in an emittinglayer, it is preferably employed in combination with one or morephosphorescent materials (triplet emitters). Phosphorescence in thesense of this invention is taken to mean the luminescence from anexcited state having a spin multiplicity >1, in particular from anexcited triplet state. For the purposes of this application, allluminescent complexes containing transition metals or lanthanoids, inparticular all luminescent iridium, platinum and copper complexes, areto be regarded as phosphorescent compounds.

The mixture comprising the compound of the formula (1) or the preferredembodiments and the emitting compound comprises between 99.9 and 1% byweight, preferably between 99 and 10% by weight, particularly preferablybetween 97 and 60% by weight, in particular between 95 and 80% byweight, of the compound of the formula (1) or the preferred embodiments,based on the entire mixture comprising emitter and matrix material.Correspondingly, the mixture comprises between 0.1 and 99% by weight,preferably between 1 and 90% by weight, particularly preferably between3 and 40% by weight, in particular between 5 and 20% by weight, of theemitter, based on the entire mixture comprising emitter and matrixmaterial. The limits indicated above apply, in particular, if the layeris applied from solution. If the layer is applied by vacuum evaporation,the same numerical values apply, with the percentage in this case beingindicated in % by vol. in each case.

A particularly preferred embodiment of the present invention is the useof the compound of the formula (1) or the preferred embodiments asmatrix material for a phosphorescent emitter in combination with afurther matrix material. Particularly suitable matrix materials whichcan be employed in combination with the compounds of the formula (1) orthe preferred embodiments are aromatic ketones, aromatic phosphineoxides or aromatic sulfoxides or sulfones, for example in accordancewith WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680,triarylamines, carbazole derivatives, for example CBP(N,N-biscarbazolylbiphenyl), m-CBP or the carbazole derivativesdisclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527or WO 2008/086851, indolocarbazole derivatives, for example inaccordance with WO 2007/063754 or WO 2008/056746, indenocarbazolederivatives, for example in accordance with WO 2010/136109 or WO2011/000455, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2010/015306, WO 2007/063754 or WO08/056746, zinc complexes, for example in accordance with EP 652273 orWO 2009/062578, fluorene derivatives, for example in accordance with WO2009/124627, diazasilole or tetraazasilole derivatives, for example inaccordance with WO 2010/054729, diazaphosphole derivatives, for examplein accordance with WO 2010/054730, or bridged carbazole derivatives, forexample in accordance with US 2009/0136779, WO 2010/050778, WO2011/042107 or WO 2011/088877. It is furthermore possible to use anelectronically neutral co-host which has neither hole-transporting norelectron-transporting properties, as described, for example, in WO2010/108579.

Particularly preferably, the compound according to formula (1) is usedas a matrix material for one or more triplet emitters in combinationwith a second host material selected from lactam compounds. Particularlypreferred are the lactam compound disclosed in WO 2011/116865, WO2011/137951, in unpublished EP 12007040.7 and in unpublished EP11008708.7. Most preferred are the compounds shown in the workingexamples of the above applications.

Examples of preferred lactam compounds to be used in combination withthe materials according to formula (1) in the emitting layer are shownin the following table.

It is likewise possible to use two or more phosphorescent emitters inthe mixture. In this case, the emitter which emits at shorter wavelengthacts as co-host in the mixture.

Suitable phosphorescent compounds (=triplet emitters) are, inparticular, compounds which emit light, preferably in the visibleregion, on suitable excitation and in addition contain at least one atomhaving an atomic number greater than 20, preferably greater than 38 andless than 84, particularly preferably greater than 56 and less than 80,in particular a metal having this atomic number. The phosphorescentemitters used are preferably compounds which contain copper, molybdenum,tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium,platinum, silver, gold or europium, in particular compounds whichcontain iridium, platinum or copper.

Examples of the emitters described above are revealed by theapplications WO 2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645,EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373, US2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO2010/102709, WO 2011/157339 or WO 2012/007086. In general, allphosphorescent complexes as used in accordance with the prior art forphosphorescent OLEDs and as are known to the person skilled in the artin the area of organic electroluminescence are suitable, and the personskilled in the art will be able to use further phosphorescent complexeswithout inventive step.

Examples of triplet emitters to be used in the devices according to thepresent application are shown in the following table.

In a further embodiment of the invention, the organic electroluminescentdevice according to the invention does not comprise a separatehole-injection layer and/or hole-transport layer and/or hole-blockinglayer and/or electron-transport layer, i.e. the emitting layer isdirectly adjacent to the hole-injection layer or the anode, and/or theemitting layer is directly adjacent to the electron-transport layer orthe electron-injection layer or the cathode, as described, for example,in WO 2005/053051. It is furthermore possible to use a metal complexwhich is identical or similar to the metal complex in the emitting layeras hole-transport or hole-injection material directly adjacent to theemitting layer, as described, for example, in WO 2009/030981.

It is furthermore possible to use the compound of the formula (1) or thepreferred embodiments both in a hole-transport layer or exciton-blockinglayer and as matrix in an emitting layer.

In the further layers of the organic electroluminescent device accordingto the invention, it is possible to use all materials as usuallyemployed in accordance with the prior art. The person skilled in the artwill therefore be able, without inventive step, to employ all materialsknown for organic electroluminescent devices in combination with thecompounds of the formula (1) according to the invention or the preferredembodiments.

Preferred fluorescent emitter materials are selected from the class ofthe arylamines. An arylamine or aromatic amine in the sense of thisinvention is taken to mean a compound which contains three substitutedor unsubstituted aromatic or heteroaromatic ring systems bonded directlyto the nitrogen. At least one of these aromatic or heteroaromatic ringsystems is preferably a condensed ring system, particularly preferablyhaving at least 14 aromatic ring atoms. Preferred examples thereof arearomatic anthracenamines, aromatic anthracenediamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position. Further preferred emitter materials are selected fromindenofluorenamines or indenofluorenediamines, for example in accordancewith WO 06/122630, benzoindenofluorenamines orbenzoindenofluorenediamines, for example in accordance with WO08/006449, and dibenzoindenofluorenamines ordibenzoindenofluorenediamines, for example in accordance with WO07/140847. Examples of emitter materials from the class of thestyrylamines are substituted or unsubstituted tristilbenamines or theemitter materials described in WO 06/000388, WO 06/058737, WO 06/000389,WO 07/065549 and WO 07/115610. Preference is furthermore given to thecondensed hydrocarbons disclosed in the application WO 10/012328.

Suitable emitter materials are furthermore the structures depicted inthe following table, and the derivatives of these structures disclosedin JP 06/001973, WO 04/047499, WO 06/098080, WO 07/065678, US2005/0260442 and WO 04/092111.

Matrix materials which can be used, preferably for fluorescent dopants,are materials from various classes of substance. Preferred matrixmaterials are selected from the classes of the oligoarylenes (forexample 2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP676461 or dinaphthyl-anthracene), in particular the oligoarylenescontaining condensed aromatic groups, the oligoarylenevinylenes (forexample DPVBi or spiro-DPVBi in accordance with EP 676461), thepolypodal metal complexes (for example in accordance with WO 04/081017),the hole-conducting compounds (for example in accordance with WO04/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO05/084081 and WO 05/084082), the atropisomers (for example in accordancewith WO 06/048268), the boronic acid derivatives (for example inaccordance with WO 06/117052) or the benzanthracenes (for example inaccordance with WO 08/145239). Suitable matrix materials are furthermorepreferably the compounds according to the invention. Apart from thecompounds according to the invention, particularly preferred matrixmaterials are selected from the classes of the oligoarylenes, comprisingnaphthalene, anthracene, benzanthracene and/or pyrene or atropisomers ofthese compounds, the oligoarylenevinylenes, the ketones, the phosphineoxides and the sulfoxides. Very particularly preferred matrix materialsare selected from the classes of the oligoarylenes, comprisinganthracene, benzanthracene, benzophenanthrene and/or pyrene oratropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

Suitable matrix materials, preferably for fluorescent dopants, are, forexample, the materials depicted in the following table, and derivativesof these materials, as disclosed in WO 04/018587, WO 08/006449, U.S.Pat. No. 5,935,721, US 2005/0181232, JP 2000/273056, EP 681019, US2004/0247937 and US 2005/0211958.

Besides the compounds according to the invention, suitablecharge-transport materials, as can be used in the hole-injection orhole-transport layer or in the electron-transport layer of the organicelectroluminescent device according to the invention, are, for example,the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4),953-1010, or other materials as are employed in these layers inaccordance with the prior art.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are applied by means of asublimation process, in which the materials are vapour-deposited invacuum sublimation units at an initial pressure of usually less than10⁻⁵ mbar, preferably less than 10⁻⁶ mbar. However, it is also possiblefor the initial pressure to be even lower, for example less than 10⁻⁷mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are applied by means of theOVPD (organic vapour phase deposition) process or with the aid ofcarrier-gas sublimation, in which the materials are applied at apressure between 10⁻⁵ mbar and 1 bar. A special case of this process isthe OVJP (organic vapour jet printing) process, in which the materialsare applied directly through a nozzle and thus structured (for exampleM. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, LITI (light induced thermalimaging, thermal transfer printing), ink-jet printing, screen printing,flexographic printing, offset printing or nozzle printing. Solublecompounds, which are obtained, for example, by suitable substitution,are necessary for this purpose. These processes are also particularlysuitable for the compounds according to the invention, since thesegenerally have very good solubility in organic solvents.

Also possible are hybrid processes, in which, for example, one or morelayers are applied from solution and one or more further layers areapplied by vapour deposition. Thus, for example, the emitting layer canbe applied from solution and the electron-transport layer by vapourdeposition.

These processes are generally known to the person skilled in the art andcan be applied by him without inventive step to organicelectroluminescent devices comprising the compounds according to theinvention.

The processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,requires formulations of the compounds according to the invention. Theseformulations can be, for example, solutions, dispersions ormini-emulsions. It may be preferred to use mixtures of two or moresolvents for this purpose. Suitable and preferred solvents are, forexample, toluene, anisole, o-, m- or p-xylene, methyl benzoate,dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP,chlorobenzene, dioxane or mixtures of these solvents. Preferably, thesolvents disclosed in WO 2010/093592 are used for the above purpose.

The present invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or mini-emulsion, comprising at leastone compound of the formula (1) or the preferred embodiments indicatedabove and at least one solvent, in particular an organic solvent. Theway in which solutions of this type can be prepared is known to theperson skilled in the art and is described, for example, in WO2002/072714, WO 2003/019694, WO 2010/093592 and the literature citedtherein.

The present invention furthermore relates to mixtures comprising atleast one compound of the formula (1) or the preferred embodimentsindicated above and at least one further compound. The further compoundcan be, for example, a fluorescent or phosphorescent dopant if thecompound according to the invention is used as matrix material. Themixture may then also additionally comprise a further material asadditional matrix material.

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby the following surprising advantages over the prior art:

-   -   1. The compounds according to the invention are very highly        suitable for use in a hole-transport or hole-injection layer in        an organic electroluminescent device. They are also suitable, in        particular, for use in a layer which is directly adjacent to a        phosphorescent emitting layer, since the compounds according to        the invention do not extinguish the luminescence.    -   2. The compounds according to the invention, employed as matrix        material for fluorescent or phosphorescent emitters, result in        very high efficiencies and long lifetimes. This applies, in        particular, if the compounds are employed as matrix material        together with a further matrix material and a phosphorescent        emitter.    -   3. The compounds according to the invention, employed in organic        electroluminescent devices, result in high efficiencies and in        steep current/voltage curves with low use and operating        voltages.

These above-mentioned advantages are not accompanied by an impairment inthe other electronic properties.

The invention is explained in greater detail by the following examples,without wishing to restrict it thereby. On the basis of thedescriptions, the person skilled in the art will be able to carry outthe invention throughout the range disclosed and prepare furthercompounds according to the invention without inventive step and use themin electronic devices or use the process according to the invention.

EXAMPLES A) Synthesis Examples

The following syntheses are carried out under a protective-gasatmosphere, unless indicated otherwise. The starting materials can bepurchased from ALDRICH or ABCR. The numbers in square brackets in thecase of the starting materials known from the literature are thecorresponding CAS numbers.

Example 1 Synthesis of the brominated spirobifluorene derivatives(Starting Materials) 1a) Synthesis of 1-bromospiro-9,9′-bifluorene

The corresponding Grignard reagent is prepared from 2.7 g (110 mmol) ofiodine-activated magnesium turnings and a mixture of 25.6 g (110 mmol)of 2-bromobiphenyl, 0.8 ml of 1,2-dichloroethane, 50 ml of1,2-dimethoxyethane, 400 ml of THF and 200 ml of toluene with secondaryheating using an oil bath at 70° C. When the magnesium has reactedcompletely, the mixture is allowed to cool to room temperature, and asolution of 25.9 g (100 mmol) of 1-bromofluorenone [36804-63-4] in 500ml of THF is then added dropwise, the reaction mixture is warmed at 50°C. for 4 h and then stirred at room temperature for a further 12 h. 100ml of water are added, the mixture is stirred briefly, the organic phaseis separated off, and the solvent is removed in vacuo. The residue issuspended in 500 ml of glacial acetic acid at 40° C., 0.5 ml of conc.sulfuric acid is added to the suspension, and the mixture issubsequently stirred at 100° C. for a further 2 h. After cooling, theprecipitated solid is filtered off with suction, washed once with 100 mlof glacial acetic acid, three times with 100 ml of ethanol each time andfinally recrystallised from dioxane. Yield: 26.9 g (68 mmol), 68%;purity about 98% according to ¹H-NMR.

1b) Synthesis of 4-bromospiro-9,9′-bifluorene

A solution of 2,2′-dibromo-biphenyl (250 g, 785 mmol) in THF (1900 ml)is treated with 318 mL of n-BuLi (2,5 M in hexane, 785 mmol) under argonat −78° C. The mixture is stirred for 30 minutes. A solution ofFluoren-9-one (144 g, 785 mmol) in 1000 mL THF is added dropwise. Thereaction proceeds at −78° C. for 30 minutes and then is stirred at roomtemperature overnight. The reaction is quenched with water and the solidis filtered. Without further purification, a mixture of the alcohol (299g, 92%) , acetic acid (2200 mL) and concentrated HCl (100 mL) isrefluxed for 2 hours. After cooling, the mixture is filtered and washedwith water and dried under vacuum. The product is isolated in the formof a white solid (280 g, 98% of theory).

The synthesis of further brominated spirobifluorene derivatives iscarried out analogously:

Product: Bromo- Bromo- Ex. Bromo-biphenyl fluorenone SpirobifluoreneYield 1c

85% 1d

90% 1e

85% 1f

90% 1g

85% 1h

90% 1i

87% 1j

85% 1k

80% 1l

80% 1m

90% 1n

80%

Example 2 Synthesis of4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

Synthesis of1-(1-biphen-4-yl)-(9,9′-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one

Tri-tert-butylphosphine (4.5 ml of a 1.0 M solution in toluene, 1,9mmol), palladium acetate (217 mg, 0.97 mmol) and sodium tert-butoxide(13.9 g, 145 mmol) are added to a solution of1-biphenyl-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (40.0 g, 111 mmol),1-Bromo-Fluoren-9-one, (25 g, 96 mmol) in degassed toluene (200 ml), andthe mixture is heated under reflux overnight. The reaction mixture iscooled to room temperature, extended with toluene and filtered throughCelite. The filtrate is evaporated in vacuo, and the residue iscrystallised from toluene/heptane The product is isolated in the form ofa pale-yellow solid (43 g, 82% of theory).

Synthesis of4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

A solution of 2-Bromo-biphenyl (17 g, 70 mmol) in THF (90 ml) is treatedwith 35 mL of n-BuLi (2,1 M in hexane, 70 mmol) under argon at -78° C.The mixture is stirred for 30 minutes. A solution of1-(1-biphen-4-yl)-(9,9′-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one (38g, 70 mmol) in 90 mL THF is added dropwise. The reaction proceeds at−78° C. for30 minutes and then is stirred at room temperature overnight.The reaction is quenched with water and extracted with ethyl acetate.The intermediate alcohol is obtained after the solvent is removed (31 g,64%). Without further purification , a mixture of the alcohol, aceticacid (700 mL) and concentrated HCl (62 mL) is refluxed for 2 hours.After cooling, the mixture is filtered and washed with water. Theresidue is crystallised from toluene. The crude product is extracted ina Soxhlet extractor (toluene) and purified by zone sublimation in vacuo.The product is isolated in the form of a pale-yellow solid (13 g, 43% oftheory, purity >99.99% according to HPLC).

Example 3a Synthesis of4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide(16.0 g, 166 mmol) are added to a solution ofbiphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (40.0 g, 111 mmol)and 4-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene(500 ml), and the mixture is heated under reflux for 2 h. The reactionmixture is cooled to room temperature, extended with toluene andfiltered through Celite. The filtrate is evaporated in vacuo, and theresidue is crystallised from ethyl acetate/heptane. The crude product isextracted in a Soxhlet extractor (toluene) and purified by zonesublimation in vacuo twice (p=3×10⁻⁴ mbar, T=298° C.). The product isisolated in the form of a pale-yellow solid (20.4 g, 27% of theory,purity >99.99% according to HPLC).

The following compounds are obtained analogously:

Ex. Br-spiro Amine Product Yield 3b

43% 3c

56% 3d

61% 3e

72% 3f

65% 3g

75% 3h

80% 3i

85% 3j

55% 3k

64% 3l

56% 3m

66% 3n

46% 3o

60% 3p

72% 3q

85% 3r

50% 3s

70% 3t

67% 3u

85% 3v

43% 3w

76% 3x

41% 3y

50% 3z

59% 3aa

71% 3ab

70% 3ac

75% 3ad

80% 3ae

85% 3af

48% 3ag

46% 3ah

41% 3ai

50% 3aj

43% 3ak

53% 3al

33% 3am

46% 3an

41% 3ao

40% 3ap

51% 3aq

47%

Example 4a Synthesis ofbiphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-4-yl)amine

a) Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine

1,1′-Bis(diphenylphosphino)ferrocene (1.5 g, 2.7 mmol), palladiumacetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol)are added to a solution of biphenyl-2-ylamine (31.0 g, 183 mmol) and2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in degassed toluene(400 ml), and the mixture is heated under reflux for 20 h. The reactionmixture is cooled to room temperature, extended with toluene andfiltered through Celite. The filtrate is extended with water,re-extracted with toluene, and the combined organic phases are dried andevaporated in vacuo. The residue is filtered through silica gel(heptane/dichloromethane) and crystallised from isopropanol.Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine is obtained in theform of a pale-yellow solid (63.0 g, 95% of theory).

b) Synthesis ofbiphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spiro-bifluoren-4-yl)amine

Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide(16.0 g, 166 mmol) are added to a solution ofbiphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (40.0 g, 111 mmol)and 4-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene(500 ml), and the mixture is heated under reflux for 2 h. The reactionmixture is cooled to room temperature, extended with toluene andfiltered through Celite. The filtrate is evaporated in vacuo, and theresidue is crystallised from ethyl acetate/heptane. The crude product isextracted in a Soxhlet extractor (toluene) and purified by zonesublimation in vacuo twice (p=3×10⁻⁴ mbar, T=298° C.). The product isisolated in the form of a pale-yellow solid (20.4 g, 27% of theory,purity >99.99% according to HPLC).

The following compounds are obtained analogously:

Starting Starting Starting Ex. material 1 material 2 material 3 ProductYield 4b

78% 4c

73% 4d

75% 4e

79% 4f

78%

Example 5a Synthesis of Synthesis ofBiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amineSynthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl(4,4,5,5tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine

102 g (198 mmol) ofBiphenyl-4-yl-(4-bromo-phenyl)-(9,9-dimethyl-9H-fluoren-2-yl)-amine, 4.8g (5.9 mmol) of Pd(dppf)Cl₂, 61.6 g (238 mmol) of bis(pinacolato)diboronand 58.3 g (594 mmol) of potassium acetate are dissolved in 1300 mL of1,4-dioxane. The reaction mixture is refluxed and agitated under anargon atmosphere for 12 hours and after cooling to room temperature, themixture is filtered through Celite. The filtrate is evaporated in vacuo,and the residue is crystallised from heptane. The product is isolated inthe form of a pale-yellow solid (87 g, 78% of theory).

Synthesis ofBiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amine

28 g (49.4 mmol) of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine, 20 g (49.4mmol) of 4-bromspirobifluorene, 1.8 g (2,5 mmol) of PdCl₂(Cy)₃, 15 g (99mmol) of cesium fluoride are dissolved in 500 mL of toluene. Thereaction mixture is refluxed and agitated under an argon atmosphere for12 hours and after cooling to room temperature, the mixture is filteredthrough Celite. The filtrate is evaporated in vacuo, and the residue iscrystallised from heptane. The crude product is extracted in a Soxhletextractor (toluene) and purified by zone sublimation in vacuo twice. Theproduct is isolated in the form of a pale-yellow solid (9 g, 24% oftheory, purity >99.99% according to HPLC).

The following compounds are synthesized analogously:

Ex. Br-Spiro Amine Product Yield 5b

43% 5c

55% 5d

60% 5e

63% 5f

70% 5g

75% 5h

55% 5i

64% 5j

60% 5k

67% 5l

58%

Example 6a 9-Spiro-4-yl-3,6-diphenyl-9H-carbazol

19.2 g (47 mmol) 4-Brom-9-spirobifluorene, 15 g (47 mmol)3,6-Diphenyl-9-H-carbazole and 29.2 g Rb₂CO₃ are suspended in 250 mLp-Xylol. To the suspension are given 0.95 g (4,2 mmol) Pd(OAc)₂ and 12.6ml of a 1M solution of Tri-tert-butylphosphine. The mixture is stirred24 h under reflux. After cooling the organic phase is separated, washedthree times with 150 mL water and is subsequently concentrated todryness in vacuo. The residue is hot extracted with toluene,recrystallized three times from toluene and subsequently sublimated athigh vacuum. Yield is 19.6 g (30.9 mmol) corresponding to 66% of theory.Purity is according to HPLC 99.9%.

The following compounds are obtained analogously:

starting material 1 starting material 2 product yield 6b

76% 6c

65% 6d

77% 6e

69%

B) Device Examples

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 2004/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

The data for various OLEDs are presented in the following Examples 1 to5 below (see Tables 1 to 7).

The substrates used are glass plates coated with structured ITO (indiumtin oxide) in a thickness of 50 nm. The OLEDs basically have thefollowing layer structure: substrate/hole-injection layer(IL)/hole-transport layer (HTL)/hole-injection layer(IL)/electron-blocking layer (EBL)/emission layer(EML)/electron-transport layer (ETL) and finally a cathode. In thedevice structure according to Table 3, the analogous structure is used,only that the first hole injection layer is omitted.

Other examples are presented with the following general device structureshown in Table 6: substrate/p-doped hole transport layer(HIL1)/hole-transport layer (HTL)/p-doped electron blocking layer(HIL2)/electron-blocking layer (EBL)/emission layer(EML)/electron-transport layer (ETL)/electron-injection layer (EIL) andfinally a cathode. The cathode is formed by an aluminium layer with athickness of 100 nm.

Other examples are presented with the following general device structureshown in Table 7. This structure differs from the structure of Examplesof Table 6 in that the second p-doped electron blocking layer isomitted, and in that a hole blocking layer (HBL) is present betweenemitting layer and electron transport layer.

The precise structures of all the OLEDs prepared in the present examplesare shown in Tables 1, 3, 6 and 7. The materials required for theproduction of the OLEDs are shown in Table 5. Data obtained are eitherin the text and/or shown in Tables 2 and 4.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or matrix materials in a certainproportion by volume by co-evaporation. An expression such as H1:SEB1(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB1 is present in the layer in aproportion of 5%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in lm/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The expression EQE @ 1000 cd/m² denotes the external quantumefficiency at an operating luminous density of 1000 cd/m². LT80 @ 6000cd/m² is the lifetime until the OLED has dropped from a luminance of6000 cd/m² to 80% of the initial intensity, i.e. to 4800 cd/m². LT80 @60 mA/cm² is the lifetime until the OLED has dropped from its initialluminance at a constant current of 60 mA to 80% of the initialluminance. The data obtained for the various OLEDs are summarised eitherin the text and/or shown in Tables 2 and 4.

Use of Compounds According to the Invention as Hole-Transport Materialsin Fluorescent and Phosphorescent OLEDs

In particular, compounds according to the invention are suitable as HIL,HTL or EBL in OLEDs. They are suitable as a single layer, but also asmixed component as HIL, HTL, EBL or within the EML.

Example 1

Singlet blue devices are shown in Tables 1 and 2, and triplet greendevices are shown in Tables 3 and 4.

Compared with devices which comprise NPB as reference (V1, V3), thesamples comprising the compounds according to the invention exhibit bothhigher efficiencies and also significantly improved lifetimes both insinglet blue and also in triplet green devices. Compared with thereference material HTMV1 (V2, V4), the compound according to theinvention HTM1 has significantly improved efficiencies and significantlybetter lifetimes.

TABLE 1 Structure of the OLEDs IL HTL IL EBL Thickness ThicknessThickness Thickness EML ETL Ex. /nm /nm /nm /nm Thickness/nmThickness/nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1 HTMV1H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nmE1 HIL1 HIL2 HIL1 HTM1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5nm 20 nm 20 nm 30 nm

TABLE 2 Data for the OLEDs EQE LT80 @ 1000 @ 6000 cd/m2 cd/m² CIE Ex. %[h] x y V1 4.8 70 0.14 0.17 V2 4.3 45 0.13 0.15 E1 6.8 130 0.13 0.16

TABLE 3 Structure of the OLEDs HTL IL EBL EML ETL Thick- Thick- Thick-Thick- Thick- ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm V3 HIL2HIL1 NPB H2(88%): ETM1(50%): 70 nm 5 nm 90 nm TEG(12%) LiQ(50%) 30 nm 40nm V4 HIL2 HIL1 HTMV1 H2(88%): ETM1(50%): 70 nm 5 nm 90 nm TEG(12%)LiQ(50%) 30 nm 40 nm E2 HIL2 HIL1 HTM1 H2(88%): ETM1(50%): 70 nm 5 nm 90nm TEG(12%) LiQ(50%) 30 nm 40 nm

TABLE 4 Data for the OLEDs Efficiency LT80 @ 1000 @ 8000 CIE Ex. cd/m2cd/m² x y V3 14.4%  85 h 0.32 0.63 V4 16.6%  60 h 0.37 0.6  E2 17.3% 195h 0.37 0.61

TABLE 5 Structures of the materials used

Example 2

In a different blue fluorescent device structure (Table 6) the referencedevices V5 and V6, using materials according to the state of the art(NPB and HTMV1), have lower efficiencies (EQE @ 10 mA/cm² of 6.2% for V5and 5.8% for V6) compared to the devices comprising the compoundsaccording to the invention E3 (8.5%), E4 (8.3%), E5 (7.9%), E6 (7.6%),E7 (7.8%), E8 (8.9%), E9 (8.4%), E10 (8.1%) and E11 (8.2%).

The reference samples V5 and V6 have also lower lifetimes (V5 of 120 h(LT80 @ 60 mA) and V6 of 105 h) compared to the samples E3 (305 h), E4(290 h), E5 (320 h), E6 (390 h), E7 (365 h), E8 (165 h), E9 (280 h), E10(285 h) and E11 (340 h).

Example 3

In a different green phosphorescent device structure (Table 6), thereference device V7 has lower efficiency (EQE @ 2 mA/cm²) of 11.7%compared to the samples comprising the compounds according to theinvention E12 (20.0%), E13 (19.6%), E14 (18.9%), E15 (19.2%) and E16(20.2%). The reference sample V6 has also lower lifetime of 80 h (LT80 @20 mA) compared to the samples E12 (90 h), E13 (185 h), E14 (105 h), E15(205 h) and E16 (185 h).

TABLE 6 Structure of the OLEDs HTL EBL EIL HIL1 Dicke/ HIL2 Dicke/ EMLETL Dicke/ Bsp. Dicke/nm nm Dicke/nm nm Dicke/nm Dicke/nm nm V5HIL3:F4TCNQ(3%) HIL3 NPB:F4TCNQ(3%) NPB H1:SEB1(5%) ETM2(50%):LiQ(50%)LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm V6 HIL3:F4TCNQ(3%) HIL3HTMV1:F4TCNQ(3%) HTMV1 H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm20 nm 20 nm 20 nm 30 nm 1 nm E3 HIL3:F4TCNQ(3%) HIL3 HTM2:F4TCNQ(3%)HTM2 H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm30 nm 1 nm E4 HIL3:F4TCNQ(3%) HIL3 HTM3:F4TCNQ(3%) HTM3 H1:SEB1(5%)ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E5HIL3:F4TCNQ(3%) HIL3 HTM4:F4TCNQ(3%) HTM4 H1:SEB1(5%) ETM2(50%):LiQ(50%)LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E6 HIL3:F4TCNQ(3%) HIL3HTM5:F4TCNQ(3%) HTM5 H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20nm 20 nm 20 nm 30 nm 1 nm E7 HIL3:F4TCNQ(3%) HIL3 HTM6:F4TCNQ(3%) HTM6H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm1 nm E8 HIL3:F4TCNQ(3%) HIL3 HTM7:F4TCNQ(3%) HTM7 H1:SEB1(5%)ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E9HIL3:F4TCNQ(3%) HIL3 HTM8:F4TCNQ(3%) HTM8 H1:SEB1(5%) ETM2(50%):LiQ(50%)LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E10 HIL3:F4TCNQ(3%) HIL3HTM9:F4TCNQ(3%) HTM9 H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20nm 20 nm 20 nm 30 nm 1 nm E11 HIL3:F4TCNQ(3%) HIL3 HTM10:F4TCNQ(3%)HTM10 H1:SEB1(5%) ETM2(50%):LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm30 nm 1 nm V7 HIL3:F4TCNQ(3%) HIL3 NPB:F4TCNQ(3%) NPB H2:TEG(10%)ETM2(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E12HIL3:F4TCNQ(3%) HIL3 HTM2:F4TCNQ(3%) HTM2 H2:TEG(10%) ETM2(50%):LiQ(50%)LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E13 HIL3:F4TCNQ(3%) HIL3HTM3:F4TCNQ(3%) HTM3 H2:TEG(10%) ETM2(50%):LiQ(50%) LiQ 20 nm 210 nm 20nm 20 nm 30 nm 40 nm 1 nm E14 HIL3:F4TCNQ(3%) HIL3 HTM4:F4TCNQ(3%) HTM4H2:TEG(10%) ETM2(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm1 nm E15 HIL3:F4TCNQ(3%) HIL3 HTM5:F4TCNQ(3%) HTM5 H2:TEG(10%)ETM2(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E16HIL3:F4TCNQ(3%) HIL3 HTM6:F4TCNQ(3%) HTM6 H2:TEG(10%) ETM2(50%):LiQ(50%)LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm

TABLE 7 Structure of the OLEDs HIL1 HTL EBL HBL EIL Dicke Dicke DickeEML Dicke ETL Dicke Bsp. /nm /nm /nm Dicke/nm /nm Dicke/nm /nm V8HIL3:F4TCNQ(3%) HIL3 H3:TEG(10%) H2 ETM2(50%):LiQ(50%) 20 nm 230 nm 40nm 5 nm 25 nm E17 HIL3:F4TCNQ(3%) HIL3 H3:HTM3(60%):TEG(10%) H2ETM2(50%):LiQ(50%) 20 nm 230 nm 40 nm 5 nm 25 nm V9 HIL3:F4TCNQ(3%) HIL3HTM3 H4:TEG(10%) ETM2(50%):LiQ(50%) LiQ 20 nm 220 nm 10 nm 40 nm 30nm 1nm E18 HIL3:F4TCNQ(3%) HIL3 HTM3 H4:HTM4(10%):TEG(10%)ETM2(50%):LiQ(50%) LiQ 20 nm 220 nm 10 nm 40 nm 30nm 1 nm E19HIL3:F4TCNQ(3%) HIL3 HTM3 H4:HTM11(45%):TEG(10%) ETM2(50%):LiQ(50%) LiQ20 nm 220 nm 10 nm 40 nm 30nm 1 nm

Use of Compounds According to the Invention as Matrix Materials inPhosphorescent OLEDs

Example 4

In a different green phosphorescent device structure (Table 7), thereference device V8, which does not have the compound according to theinvention as a matrix material of the emitting layer, has lowerefficiency (EQE @ 2 mA/cm² of 14.4%) compared to the sample E17comprising the compound according to the invention HTM3 (EQE @ 2 mA/cm²of 16.1%), used as a mixed matrix component in the EML. The referencesample V8 has also lower lifetime of 305 h (LT80 @ 20 mA) compared tosample E17 of 330 h.

Example 5

In a different green phosphorescent device structure (Table 7) it isshown that the compounds according to the invention show favorableeffects as a mixed matrix component in the emitting layer, incombination with a lactam compound H4. The reference device V9 has anefficiency (EQE @ 2 mA/cm²) of 17.6% and a lifetime of 255 h. Lifetimecan be improved by adding a compound according to the invention to theemitting layer as a co-matrix material, as shown by examples E18 and E19compared to V9. Device E18 shows an efficiency of 13.4% and a lifetimeof 400 h, and device E19 shows an efficiency of 17.9% and a lifetime of270 h, which are both improvements compared to reference device V9.

1-15. (canceled)
 16. A compound of the following formula (1):

where the following applies to the symbols and indices used: Ar¹ is oneach occurrence, identically or differently, an aromatic orheteroaromatic ring system having 6 to 60 C atoms, selected from thegroup consisting of fluorene, spirobifluorene, biphenyl, terphenyl,quaterphenyl, carbazole, dibenzofuran and dibenzothiophene, each ofwhich may also be substituted by one or more radicals R⁵; Ar¹ and Ar²here may also be connected to one another by a group E; Ar² is on eachoccurrence, identically or differently, an aromatic or heteroaromaticring system having 6 to 60 C atoms, which may in each case also besubstituted by one or more radicals R⁵; Ar¹ and Ar² here may also beconnected to one another by a group E; Ar^(S) is on each occurrence,identically or differently, an aromatic or heteroaromatic ring systemhaving 6 to 60 C atoms, which may in each case also be substituted byone or more radicals R⁵; E is on each occurrence, identically ordifferently, a single bond, C(R⁵)₂, NR⁵, O or S; R¹, R², R³, R⁴ areselected on each occurrence, identically or differently, from the groupconsisting of H, D, F, Cl, Br, I, CN, Si(R⁶)₃, a straight-chain alkyl,alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclicalkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of whichmay be substituted by one or more radicals R⁶, where in each case one ormore non-adjacent CH₂ groups may be replaced by Si(R⁶)₂, C═NR⁶,P(═O)(R⁶), SO, SO₂, NR⁶, O, S or CONR⁶ and where one or more H atoms maybe replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ringsystem having 6 to 60 C atoms, which may in each case be substituted byone or more radicals R⁶, an aryloxy or heteroaryloxy group having 5 to60 aromatic ring atoms, which may be substituted by one or more radicalsR⁶, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁶,where two or more adjacent substituents R¹ or R² or R³ or R⁴ mayoptionally form a mono- or polycyclic, aliphatic ring system, which maybe substituted by one or more radicals R⁶; R⁵ is selected on eachoccurrence, identically or differently, from the group consisting of H,D, F, Cl, Br, I, CN, Si(R⁶)₃, a straight-chain alkyl, alkoxy orthioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl,alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may besubstituted by one or more radicals R⁶, where in each case one or morenon-adjacent CH₂ groups may be replaced by Si(R⁶)₂, C═NR⁶, P(═O)(R⁶),SO, SO₂, NR⁶, O, S or CONR⁶ and whereone or more H atoms may be replacedby D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6to 60 C atoms, which may in each case be substituted by one or moreradicals R⁶, an aryloxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which may be substituted by one or more radicals R⁶, or anaralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, whichmay in each case be substituted by one or more radicals R⁶, where two ormore adjacent substituents R⁵ may optionally form a mono- or polycyclic,aliphatic ring system, which may be substituted by one or more radicalsR⁶; R⁶ is selected from the group consisting of H, D, F, an aliphatichydrocarbon radical having 1 to 20 C atoms or an aromatic orheteroaromatic ring system having 5 to 30 C atoms, in which one or moreH atoms may be replaced by D or F, where two or more adjacentsubstituents R⁶ may form a mono- or polycyclic, aliphatic ring systemwith one another; i is on each occurrence, identically or differently, 0or 1; m is 0, 1 or 2; n is on each occurrence, identically ordifferently, 0, 1, 2, 3 or 4; p is 1; q is 0; r, s are on eachoccurrence, identically or differently, 0, 1, 2, 3 or 4, where p+r≤4 andq+s≤4; or compound of a formula (1), with the proviso that the followingdefinitions apply to groups Ar¹ and Ar² instead of the definitionsabove: Ar¹ and Ar² are connected to each other via a group E, as definedabove, and groups Ar¹ and Ar² are, identically or differently on eachoccurrence, an aromatic or heteroaromatic ring system having 6 to 60 Catoms, which may in each case also be substituted by one or moreradicals R⁵.
 17. The compound according to claim 16, wherein i is
 0. 18.The compound according to claim 16, selected from compounds of thefollowing formulae (3), (6) and (9),

where the symbols and indices used are defined as in claim
 16. 19. Thecompound according to claim 16, selected from compounds of the followingformulae (3a), (6a) and (9a),

where the symbols and indices used are defined as in claim
 16. 20. Thecompound according to claim 16, selected from compounds of the followingformulae (3b), (6b) and (9b),

where the symbols used are defined as in claim
 16. 21. The compoundaccording to claim 16, wherein groups Ar1 and Ar2 are not connected toone another by a group E and are selected, identically or differently oneach occurrence, from the groups of the following formulae (11) to (66),

where the dashed bond indicates the bond to the nitrogen, and the groupsmay be substituted by one or more radicals R⁵.
 22. The compoundaccording to claim 21, wherein Ar¹ and Ar²are selected, identically ordifferently on each occurrence, from the groups of the formulae (11),(20) and (24), which may be substituted by one or more radicals R⁵. 23.The compound according to claim 16, wherein the groups Ar¹ and Ar² areselected differently from one another.
 24. The compound according toclaims 16, wherein R¹ to R⁴ are selected, identically or differently oneach occurrence, from the group consisting of H, F, CN, a straight-chainalkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclicalkyl or alkoxy group having 3 to 10 C atoms, each of which may besubstituted by one or more radicals R⁶, where one or more non-adjacentCH₂ groups may be replaced by O and where one or more H atoms may bereplaced by F, an aromatic or heteroaromatic ring system having 6 to 24aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁶.
 25. The compound according to claim 16, wherein theradical R⁵ which is bonded to Ar¹ or Ar² or Ar^(S) is selected,identically or differently on each occurrence, from the group consistingof H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, abranched or cyclic alkyl group having 3 to 10 C atoms or an aromatic orheteroaromatic ring system having 5 to 24 aromatic ring atoms, each ofwhich may be substituted by one or more radicals R⁶.
 26. The compoundaccording to claim 16, wherein Ar¹ and Ar² are not connected to oneanother by a group E.
 27. The compound according to claim 16, whereinindices m, s, r and n are
 0. 28. The compound according to claim 21,wherein Ar¹, Ar² are, identically or differently, a group of one of theformulae (11) to (66); Ar¹ and Ar² are not connected to one another by agroup E; R5 is, if the radical R5 is bonded to Ar1 or Ar2 or ArS,selected, identically or differently on each occurrence, from the groupconsisting of H, F, CN, a straight-chain alkyl group having 1 to 10 Catoms, a branched or cyclic alkyl group having 3 to 10 C atoms or anaromatic or heteroaromatic ring system having 5 to 24 aromatic ringatoms, each of which may be substituted by one or more radicals R6; orR5 which is bonded to the carbon bridge in the formulae (20) to (23),(53), and (54), is, identically or differently, an alkyl group having 1to 10 C atoms, in particular methyl, or a phenyl group, which may besubstituted by one or more radicals R6; or R⁵ which is bonded to thenitrogen bridge in the formulae (28) to (31), (40) to (43) or (55) to(58), and (63) to (66) is a phenyl group, which may be substituted byone or more radicals R⁶; R⁶ is selected on each occurrence, identicallyor differently, from the group consisting of H, a straight-chain alkylgroup having 1 to 10 C atoms or a branched or cyclic alkyl group having3 to 10 C atoms or an aromatic ring system having 6 to 24 C atoms; i is0; m is 0; n is 0; r is 0; s is
 0. 29. A process for the preparation ofthe compound of claim 16, wherein the diarylamino group is introduced bya C—N coupling reaction between a 1- or 3- or 4-halogenatedspirobifluorene and a diarylamine.
 30. A method comprising utilizing thecompound according to claim 16 in an electronic device.
 31. AnElectronic device comprising at least one compound according to claim16, selected from the group consisting of organic electroluminescentdevices, organic integrated circuits, organic field-effect transistors,organic thin-film transistors, organic light-emitting transistors,organic solar cells, organic dye-sensitised solar cells, organic opticaldetectors, organic photoreceptors, organic field-quench devices,light-emitting electrochemical cells, organic laser diodes and organicplasmon emitting devices.
 31. Electronic device according to claim 30,selected from organic electroluminescent devices, wherein the compoundis comprised as hole-transport material in a hole-transport orhole-injection or exciton-blocking or electron-blocking layer, or iscomprised as matrix material for fluorescent or phosphorescent emittersin an emitting layer.
 32. The compound according to claim 16, whereinthe compound is of formula (1-1)

where the symbols and indices used are defined as in claim 16.